EP2322530B1 - Gruppe-4-Metallvorläufer für metallhaltige Filme - Google Patents

Gruppe-4-Metallvorläufer für metallhaltige Filme Download PDF

Info

Publication number
EP2322530B1
EP2322530B1 EP10188585.3A EP10188585A EP2322530B1 EP 2322530 B1 EP2322530 B1 EP 2322530B1 EP 10188585 A EP10188585 A EP 10188585A EP 2322530 B1 EP2322530 B1 EP 2322530B1
Authority
EP
European Patent Office
Prior art keywords
group
bis
precursor
metal
titanium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP10188585.3A
Other languages
English (en)
French (fr)
Other versions
EP2322530A3 (de
EP2322530A2 (de
Inventor
Sergei Vladimirovich Ivanov
Xinjian Lei
Hansong Cheng
Daniel P. Spence
Moo-Sung Kim
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Air Products and Chemicals Inc
Original Assignee
Air Products and Chemicals Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Air Products and Chemicals Inc filed Critical Air Products and Chemicals Inc
Publication of EP2322530A2 publication Critical patent/EP2322530A2/de
Publication of EP2322530A3 publication Critical patent/EP2322530A3/de
Application granted granted Critical
Publication of EP2322530B1 publication Critical patent/EP2322530B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic System without C-Metal linkages
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/405—Oxides of refractory metals or yttrium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • MOS metal oxide semiconductor
  • IC integrated circuits
  • field effect semiconductor devices produce an output signal that is proportional to the width of the channel, such that scaling reduces their output.
  • This effect has generally been compensated for by decreasing the thickness of the gate dielectric, thus bringing the gate in closer proximity to the channel and enhancing the field effect, which thereby increases the drive current. Therefore, it has become increasingly important to provide extremely thin, reliable and low-defect gate dielectrics for improving device performance.
  • a thermal silicon oxide, SiO 2 has been the primary gate dielectric, because it is compatible with the underlying silicon substrate, and its fabrication process is relatively simple.
  • the silicon oxide gate dielectric has a relatively low dielectric constant (k), 3.9, further scaling down of silicon oxide gate dielectric thickness to less than 10 ⁇ (1 nm) has become more and more difficult, especially due to gate-to-channel leakage current through the thin silicon oxide gate dielectric.
  • EOT equivalent oxide thickness
  • high-k metal oxide materials have been proposed as the alternative dielectric materials for gate or capacitor dielectrics.
  • Group 4-containing precursors may also be used by themselves or combined with other metal-containing precursors to make high dielectric constant and/or ferroelectric oxide thin films such as, for example, Pb(Zr,Ti)O 3 or (Ba,Si)(Zr,Ti)O 3 . Because the dielectric constant of metal oxide materials can be made greater than that of the silicon oxide, a thicker metal oxide layer having a similar EOT can be deposited.
  • Group 4 precursors such as, for example, titanium-containing, zirconium-containing, and hafnium-containing precursors and combinations thereof, to be able to deposit metal-containing films such as, but not limited to, oxide, nitride, silicate or combinations thereof on substrates, such as metal nitride or silicon.
  • high-k metal oxide materials presents several problems, when using traditional substrate materials, such as silicon.
  • the silicon can react with the high-k metal oxide or be oxidized during deposition of the high-k metal oxide or subsequent thermal processes, thereby forming an interface layer of silicon oxide. This increases the equivalent oxide thickness, thereby degrading device performance. Further, an interface trap density between the high-k metal oxide layer and the silicon substrate is increased. Thus, the channel mobility of the carriers is reduced. This reduces the on/off current ratio of the MOS transistor, thereby degrading its switching characteristics.
  • the high-k metal oxide layer such as a hafnium oxide (HfO 2 ) layer or a zirconium oxide (ZrO 2 ) layer, has a relatively low crystallization temperature and is thermally unstable.
  • the metal oxide layer can be easily crystallized during a subsequent thermal annealing process for activating the dopants injected into source/drain regions. This can form grain boundaries in the metal oxide layer, through which current can pass.
  • the leakage current characteristics may deteriorate.
  • the crystallization of the high-k metal oxide layer undesirably affects a subsequent alignment process due to irregular reflection of the light on an alignment key having the rough surface.
  • Group 4 metal-containing films can be deposited using chemical vapor deposition (CVD) and/or atomic layer deposition (ALD) processes.
  • CVD chemical vapor deposition
  • ALD atomic layer deposition
  • the vapors of one or more volatile precursors are introduced into a chemical vapor deposition reactor loaded with a semi-fabricated substrate, which has been pre-heated to the temperature above the thermal decomposition of at least one of the precursors.
  • the rate of film growth is determined by the rate of reaction between the reactants on the surface, and the film growth continues, as long as reactant vapors are present in the vapor phase.
  • ALD atomic layer deposition
  • reactants are introduced into an ALD reactor sequentially, thus avoiding any gas phase reactions between the reactants.
  • a typical cycle of ALD processes for deposition metal oxide films includes: 1) introducing enough vapors of a metal containing precursor to the ALD chamber to allow the precursor to chemically adsorb on the surface until the whole surface area is covered; 2) purging the ALD chamber with inert gas to remove any by-products as well as unreacted precursors; 3) introducing an oxidizer to react with the precursor adsorbed on the surface; 4) purging away any unreacted oxidizer and any reaction by-products.
  • the cycle is repeated until a desired thickness is achieved.
  • An ideal ALD process is self-limiting, i.e. the substrate surface is saturated with a reactant during its introduction and the film growth stops even though large excess of precursors are present in the gas phase. Therefore, ALD provides multiple advantages over CVD for deposition of highly conformal films on complex surfaces, such as deep trenches and other stepped structures
  • the balance between good thermal stability of ALD precursors and the ability of ALD precursors to chemisorb on the substrate surface is very important for producing thin, conformal films of high K dielectric metal oxides. It is desirable that the precursors are thermally stable during vapor delivery in order to avoid premature decomposition of the precursor, before it reaches the vapor deposition chamber during processing. Premature decomposition of the precursor, not only results in undesirable accumulation of side products that would clog fluid flow conduits of the deposition apparatus, but also may cause undesirable variations in composition or as well as dielectric constant and/or ferroelectric properties of the deposited metal oxide thin film.
  • a number of various delivery systems have been developed for the delivery of precursors to CVD or ALD reactors.
  • DI direct liquid injection
  • a liquid precursor or a solution of a precursor in a solvent is delivered to a heated vaporization system, whereby the liquid composition is transferred from the liquid phase into the gas phase.
  • Advanced liquid metering of the precursor to the vaporizer provides accurate, stable control of precursor delivery rate.
  • it is critical during the vaporization process that the precursor structure is maintained and decomposition is eliminated.
  • Another method which is already widely used in semiconductor industry for delivery of metal organic precursors, is based on conventional bubbler technology, where inert gas is bubbled through a neat liquid or a molten precursor at elevated temperature.
  • precursors typically have low vapor pressure and have to be heated to 100-200°C to deliver enough precursor vapors to the deposition reactor by the bubbling method.
  • Solid precursors delivered from their molten phase may plug the lines during multiple cooling/heating cycles. It is desired that precursors are liquids or solids with melting point significantly lower than the bubbler temperature. Products of thermal decomposition may also plug delivery lines and affect the delivery rate of precursors. Extended periods of time at the bubbler temperatures may also cause thermal decomposition of the precursors.
  • the precursors may also react with traces of moisture and oxygen introduced to the bubbler during multiple deposition cycles. It is highly desirable that the precursors maintain their chemical identity over time during storage and delivery. Any change in chemical composition of a Group 4 precursor is deleterious, because it may impair the ability of the vapor deposition process to achieve constant delivery and film growth.
  • Prior art in the field of the present invention includes: US 6,603,033 ; Chem. Vap. Deposition, 9, 295 (2003 ); J. of Less Common Metals, 3, 253 (1961 ); J. Am. Chem. Soc. 79, p4344-4348 (1957 ); Journal of the Chemical Society A: Inorganic, Physical, and Theoretical Chemistry: 904-907 (1970 ); Chemical Communications 10(14): 1610-1611 (2004 ); Journal of Materials Chemistry 14, 3231-3238 (2004 ); Chemical Vapor Deposition 12, 172-180 (2006 ); JP 2007/197804A ; JP 10/114781A ; WO 1984/003042A1 ; JP 28/22946B2 ; US 6,562,990 B ; WO 96/40690 ; US 2010/0018439 A ; and Applicants' co-pending application US 2007/0248754A1 , US Serial No.
  • the Group 4 precursors in the prior art are mostly solid and have relatively low vapor pressure (e.g., 0.5 torr (67 Pa) or below at the delivery temperature).
  • these precursors are not thermally stable at temperatures greater than 150°C, thus causing delivery or process issues during semiconductor manufacturing, which can include, but are not limited to, lower ALD process window, clogging of the delivery lines between the source container and reactor, and particle deposition on the wafers.
  • Group 4 precursors preferably liquid Group 4 precursors, which exhibit at least one of the following properties: lower molecular weight (e.g., 500 mass units (m.u.) or below), lower melting point (e.g., 60°C or below), high vapor pressure (e.g., 0.5 torr (67 Pa) or greater).
  • Group 4 precursors having high ALD thermal window e.g., 300 °C and above
  • high ALD growth rate e.g. above ⁇ 0.3 A/cycle (0.03 nm/cycle)
  • Group 4 precursors which are thermally stable and which maintain their chemical composition during storage and delivery.
  • the present invention is a family of Group 4 metal precursors represented by the formula: M(OR 1 ) 2 (R 2 C(OO)C(R 3 )C(O)OR 1 ) 2 ; also illustrated schematically as: wherein M is a Group 4 metal selected from the group consisting of Ti, Zr, and Hf; wherein R 1 is selected from the group consisting of linear or branched alkyl groups containing 1 to 10 carbon atoms and aryl groups containing 6 to 12 carbon atoms, and is preferably selected from methyl, ethyl, and n-propyl, particularly when M is Ti; R 2 can be selected from the group consisting of branched C 3-10 alkyls and C 6-12 aryls, and is preferably selected from iso-propyl, tert-butyl, sec-butyl, iso-butyl, and tert-amyl; and R 3 is selected from the group consisting of hydrogen, C 1-10 alkyls, and C 6-12 ary
  • the precursors have common alkoxy groups, thus all R1 groups are chosen to have the same meaning.
  • the precursor is a liquid at room temperature and pressure, e.g. about 20°C and about 1 bar, or a solid with melting point below 60°C.
  • Group 4 metal precursors preferably liquid or low melting point Group 4 metal precursors, that are suitable, for example, as precursors in chemical vapor deposition, cyclical chemical vapor deposition (CCVD) or atomic layer deposition processes.
  • the complexes and compositions are useful for fabricating metal-containing films on substrates, such as silicon, metal nitride, metal oxide, metal oxynitride, metal silicate, and other metal containing layers via chemical vapor deposition (CVD), cyclical chemical vapor deposition (CCVD) or atomic layer deposition (ALD) processes
  • the deposited metal-containing films have applications ranging from computer chips, optical device, magnetic information storage, to metal-containing catalyst coated on a supporting material.
  • a number of Group 4 mixed-ligand metal precursors containing alkoxy, diketonate, ketoesterate, cyclopentadienyl ligands have been proposed for deposition of metal oxide films.
  • Using complexes with different ligands permits the modification of physical properties and chemical reactivity of precursors.
  • one potential problem of precursors containing different ligands is that ligand exchange during storage or delivery may result in the formation of a mixture of compounds having different volatility and reactivity.
  • Careful design of the precursor's chemical structure is required to optimize precursor performance in CVD, CCVD or ALD deposition, as well as avoiding potential inter- as well as intramolecular ligand exchange reactions when delivery is at higher temperature.
  • a Group 4 metal precursor represented by the formula: M(OR 1 ) 2 (R 2 C(O)C(R 3 )C(O)OR 1 ) 2 , also depicted in 2-dimensions as: wherein M is a Group 4 metal selected from the group consisting of Ti, Zr, and Hf; R 1 is selected from the group consisting of linear or branched C 1-10 alkyls and C 6-12 aryls, and is preferably selected from methyl, ethyl or n-propyl; R 2 is selected from the group consisting of branched C 3-10 alkyls and C 6-12 aryls, and is preferably selected from iso-propyl, tert-butyl, sec-butyl, iso-butyl or tert-amyl; R 3 is selected from the group consisting of hydrogen, C 1-10 alkyls, and C 6-12 aryls, and is preferably selected from hydrogen or methyl.
  • Figure 3 shows 1 H NMR spectra of bis(methoxy)bis(methyl 4,4-dimethyl-3-oxopentanoato)titanium before and after heating for one hour at 200°C, indicating no changes in its composition after thermal treatment, and thus, very good thermal stability of this precursor. No changes in 1 H NMR spectra after heating for one hour at 200°C were also observed during thermal study of other precursors, where the R 1 groups are the same, for example bis(n-propoxy)bis(n-propyl 4,4-dimethyl-3-oxopentanoato)titanium.
  • Figure 6 shows 1 H NMR spectra of d 8 -toluene solutions of bis(methoxy)bis(n-propyl 4,4-dimethyl-3-oxopentanoato)titanium before and after heating for one hour at 200 °C in which there are two kinds of alkoxy groups, i.e. methoxy and n-propoxy.
  • Presence of at least two sets of OCH 3 groups (attributed to methoxy and methyl 4,4-dimethyl-3-oxopentanoato ligand) and at least two sets of (OCH 2 CH 2 CH 3 ) groups (attributed to n-propoxy and n-propyl 4,4-dimethyl-3- oxopentanoato ligands) suggests ligand exchange of methoxy and n-propoxy groups between ketoesterate and methoxy ligands, and the formation of a mixture of precursors having two different ketoesterate ligands, as shown below. This type of exchange results in metal precursor complexes having the same molecular weight, but different ketoesterate ligands and different volatility and chemical reactivity.
  • Figure 5 shows 1 H NMR spectra of d 8 -toluene solutions of: (a) bis(methoxy)bis(methyl 4,4-dimethyl-3-oxopentanoato)titanium, top graph, (b) bis(n-propoxy)bis(n-propyl 4,4-dimethyl-3-oxopentanoato)titanium, middle graph, and their (c) mixture, bottom graph.
  • Figure 1 demonstrates that Group 4 metal complexes having different combination of alkoxy and ketoesterate ligands have different volatility (boiling points)
  • R 2 is selected from the group consisting of branched C 3-10 alkyls or aryls, preferably iso-propyl, iso-butyl, sec-butyl, tert-butyl or tert-amyl. Without being bound by any particular theory, it is believed that steric hindrance of the branched alkyl group, R 2 , provides better thermal stability for the precursors of this invention.
  • Figure 4 shows the comparison of differential scanning calorimetry (DSC) in high pressure sealed capsules at 10 °C/min heating rate of bis(ethoxy)bis(ethyl 4,4-dimethyl-3-oxopentanoato)titanium (a precursor of this invention wherein R 2 is tert-butyl) and bis(ethoxy)bis(ethyl acetoacetato)titanium (wherein R 2 is methyl).
  • DSC differential scanning calorimetry
  • DSC data show much better thermal stability of the precursor of this invention, where R 2 is branched (exotherm onset is 310 °C) compare to bis(ethoxy)bis(ethyl acetoacetato)titanium, wherein R 2 is a linear alkyl (exotherm onset is 278 °C).
  • a family of Group 4 metal precursors is represented by the formula: M(OR 1 ) 2 ( t BuC(O)CHC(O)OR 1 ) 2 , also depicted in 2-dimensions as: wherein M is a Group 4 metal selected from the group consisting of Ti, Zr, and Hf; wherein R 1 is selected from the group consisting of linear or branched C 1-10 alkyls and C 6-12 aryls, preferably methyl, ethyl, and n-propyl.
  • a family of Group 4 metal precursors is represented by the formula: Ti(OR 1 ) 2 ( t BuC(O)CHC(O)OR 1 ) 2 also depicted in 2-dimensions as: wherein R 1 is selected from the group consisting of methyl, ethyl, and propyl.
  • the Group 4 metal precursor exhibits at least one of the following properties: low molecular weight (e.g., 500 m.u. or below), low viscosity (600 cP and below), low melting point (e.g., 60°C or below), and high vapor pressure (e.g., 0.5 torr (67 Pa) or greater).
  • low molecular weight e.g., 500 m.u. or below
  • low viscosity 600 cP and below
  • low melting point e.g., 60°C or below
  • high vapor pressure e.g., 0.5 torr (67 Pa) or greater.
  • the Group 4 metal containing film may be a metal containing oxide film; metal containing nitride film, metal containing oxynitride film, metal containing silicate film, multi-component metal oxide film, and any combination or laminate thereof, which may be used, for example, in fabricating semiconductor devices.
  • the method disclosed herein provides a Group 4 metal or multi-component metal oxide film that has a dielectric constant substantially higher than that of any of: conventional thermal silicon oxide, silicon nitride, or zirconium/hafnium oxide dielectric.
  • the method disclosed herein preferably deposits the Group 4 metal containing films using atomic layer deposition (ALD) or chemical vapor deposition (CVD) processes.
  • suitable deposition processes for the method disclosed herein include, but are not limited to, cyclic CVD (CCVD), MOCVD (Metal Organic CVD), thermal chemical vapor deposition, plasma enhanced chemical vapor deposition (PECVD), high density PECVD, photon assisted CVD, plasma-photon assisted (PPECVD), cryogenic chemical vapor deposition, chemical assisted vapor deposition, hot-filament chemical vapor deposition, CVD of a liquid polymer precursor, deposition from supercritical fluids, and low energy CVD (LECVD).
  • the metal containing films are deposited via plasma enhanced ALD (PEALD) or plasma enhanced cyclic CVD (PECCVD) process.
  • the deposition temperature may be relatively lower, or may range from 200°C to 400°C, and may allow for a wider process window to control the specifications of film properties required in end-use applications.
  • Exemplary deposition temperatures for the PEALD or PECCVD deposition include ranges having any one of the following endpoints: 200, 225, 250, 275, 300, 325, 350, 375, and 400 °C.
  • a Group 4 metal silicate or metal silicon oxynitride film is formed onto at least one surface of a substrate using a Group 4 metal precursor of Formula A, a silicon-containing precursor, an oxygen source, and optionally a nitrogen source.
  • metal-containing and silicon-containing precursors typically react in either liquid form or gas phase, thereby preventing film formation
  • the method disclosed herein typically avoids pre-reaction of the metal containing and silicon-containing precursors by using ALD or CCVD methods that separate the precursors prior to and/or during the introduction to the reactor.
  • deposition techniques such as an ALD or CCVD processes, are used to deposit the metal-containing film.
  • an ALD process is used to deposit the metal-containing film.
  • the film is deposited by exposing the substrate surface alternatively to the metal precursor or the silicon-containing precursors. Film growth proceeds by self-limiting control of surface reaction, the pulse length of each precursor, and the deposition temperature. However, once the surface of the substrate is saturated, the film growth ceases.
  • the metal-containing film may be deposited using a CCVD process. In this embodiment, the CCVD process may be performed using a higher temperature range than the ALD window, or from 350°C to 600°C.
  • Exemplary deposition temperatures for the CCVD deposition include ranges having any one of the following endpoints (provided in degrees Celsius): 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, 500, 525, 550, 575, and 600 °C.
  • precursors of this invention can be particularly useful for ALD of metal containing films.
  • Precursors of this invention may have an ALD operating thermal window greater than 350°C, and ALD growth rates higher than 0.3 ⁇ /cycle (0.03 nm/cycle), preferably greater than 0.5 ⁇ /cycle (0.05 nm/cycle).
  • the method disclosed herein forms the metal oxide films using group 4 metal precursors and an oxygen source.
  • the oxygen source can be selected from the group consisting of oxygen, plasma oxygen, nitrous oxide, ozone, water, plasma water, and mixture thereof.
  • the method disclosed herein forms the metal containing films using at least one metal precursor, such as the Group 4 metal containing precursors described herein, optionally at least one silicon-containing precursor, optionally an oxygen source, optionally an additional metal-containing or other metal-containing precursor, optionally a reducing agent, and optionally a nitrogen source.
  • the precursors and sources used herein may sometimes be described as "gaseous", it is understood that the precursors can be either liquid or solid, which are transported with or without an inert gas into the reactor via direct vaporization, bubbling or sublimation. In some case, the vaporized precursors can pass through a plasma generator.
  • metal containing precursors can be used in addition to the Group 4 metal precursors described herein.
  • Metals commonly used in semiconductor fabrication, that can be used as the metal component for a metal amide include: titanium, tantalum, tungsten, hafnium, zirconium, cerium, zinc, thorium, bismuth, lanthanum, strontium, barium, lead, and combinations thereof.
  • Examples of other metal containing precursors, that may be used with the method disclosed herein include, but are not limited to: tetrakis(dimethylamino)zirconium (TDMAZ), tetrakis(diethylamino)zirconium (TDEAZ), tetrakis(ethylmethylamino)zirconium (TEMAZ), tetrakis(dimethylamino)hafnium (TDMAH), tetrakis(diethylamino)hafnium (TDEAH), and tetrakis(ethylmethylamino)hafnium (TEMAH), tetrakis(dimethylamino)titanium (TDMAT), tetrakis(diethylamino)titanium (TDEAT), tetrakis(ethylmethylamino)titanium (TEMAT), tert-butylimino tri(diethylamino)
  • the metal containing precursors that can be used in addition to the Group 4 metal precursors described herein to provide a metal-containing film, are polydentate ⁇ -ketoiminates which are described, for example, in Applicants' co-pending application US2007/0248754A1 , US Serial No. 11/945678 filed on November 27, 2007 , Applicants' co-pending application U.S. Serial No. 12/266,806 which was filed on November 11, 2008 Applicants' patents US 7,691,984 , US7,723,493 , all of which are incorporated herein by reference in their entirety.
  • the polydentate ⁇ -ketoiminates may incorporate an alkoxy group in the imino group.
  • the polydentate ⁇ -ketoiminates are selected from the group represented by the following Formula F and G: wherein M is a Group 2 metal such as, for example, magnesium, calcium, strontium, and barium. Preferably, M is strontium or barium.
  • the organo groups (i.e., the R 1-5 groups) employed in the complexes of Formula F may include a variety of organo groups and they may be linear or branched.
  • R 1 is selected from the group consisting of: a C 1-10 alkyl, a C 1-10 alkoxyalkyl, a C 1-10 alkoxy, a C 1-10 fluoroalkyl, a C 1-10 cycloaliphatic, and a C 6-10 aryl.
  • alkoxyalkyl refers to an ether-like moiety that includes a C-O-C fragment. Examples include -CH 2 CH 2 -O-CH 2 CH 2 -O-CH 3 and -CH 2 CH 2 -O-CH 2 -O-CH 3 .
  • R 1 is a bulky alkyl group containing 4 to 6 carbon atoms, such as, for example; a tert -butyl group, a sec -butyl, and a tert -pentyl group.
  • the most preferred R 1 group is tert -butyl or tert -pentyl.
  • R 2 is selected from the group consisting of: hydrogen, a C 1-10 alkyl, a C 1-10 alkoxyalkyl, a C 1-10 alkoxy, a C 3-10 cycloaliphatic, and a C 6-10 aryl. More preferably, R 2 is hydrogen, or a C 1-2 alkyl.
  • R 3 is selected from the group consisting of: a C 1-10 alkyl, a C 1-10 alkoxyalkyl, a C 1-10 alkoxy, a C 3-10 cycloaliphatic, and a C 6-10 aryl. More preferably, R 3 is a C 1-2 alkyl.
  • R 4 is a C 1-6 linear or branched alkylene and, more preferably, R 4 contains a branched alkylene bridge containing C 3-4 and having at least one chiral center carbon atom. Without intending to be bound by a particular theory, it is believed that the chiral center in the ligand plays a role in lowering the melting point, as well as increasing the thermal stability of the complex.
  • R 5 is selected from the group consisting of: a C 1-10 alkyl, a C 1-10 fluoroalkyl, a C 3-10 cycloaliphatic, and a C 6-10 aryl. More preferably, R 5 is a C 1-2 alkyl.
  • M is a metal group having a valence of from 2 to 5 wherein R 1 is selected from the group consisting of alkyl, alkoxyalkyl, fluoroalkyl, cycloaliphatic, and aryl, having C 1-10 carbon atoms; R 2 is selected from the group consisting of hydrogen, C 1-10 alkyl, C 1-10 alkoxy, C 4-10 cycloaliphatic, and C 6-12 aryl; R 3 is selected from the group consisting of C 1-10 alkyl, C 1-10 alkoxyalkyl, C 1-10 fluoroalkyl, C 4-10 cycloaliphatic, and C 6-12 aryl; R 4 is a C 3-10 linear or branched alkyl bridge, preferably R 4 is having at least one chiral carbon atom; R 5-6 are individually selected from the group consisting of C 1-10 alkyl, C 1-10 fluoroalkyl, C 4-10 cycl
  • metal precursors of this invention can be used in addition to at least one metal-ligand complex, wherein one or more ligands of the metal-ligand complex are selected from the group consisting of ⁇ -diketonates, ⁇ -diketoesterate, ⁇ -ketoiminates, ⁇ -diiminates, alkyls, carbonyl, alkyl carbonyl, cyclopentadienyls, pyrrolyl, imidazolyl, amidinate, alkoxy, and mixtures thereof, wherein the ligand can be monodentate, bidentate and multidentate, and the metal of the metal-ligand complex is selected from Group 2 to 16 elements of the Periodic Table of the Elements.
  • these complexes comprise: bis(2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanonato-N,O,N')strontium, bis(2,2-dimethyl-5-(1-dimethylamino-2-propylimino)-3-hexanonato-N,O,N')strontium, tetrakis(2,2,6,6-tetramethyl-3,5-heptanedionato)cerium (IV), tris(2,2,6,6-tetramethyl-3,5-heptanedionato)lanthanum, Sr[( t Bu) 3 Cp] 2 , Sr[( i Pr) 3 Cp] 2 , Sr[( n PrMe 4 Cp] 2 , Ba[( t Bu) 3 Cp] 2 , LaCp 3 , La(MeCp) 3 , La(EtCp) 3 , La( i PrCp)
  • metal precursors of this invention can be used for deposition of titanium oxide, doped titanium oxide, doped zirconium oxide, strontium titanate (STO) and barium strontium titanate (BST).
  • the deposition process further involves the introduction of at least one silicon-containing precursor.
  • silicon-containing precursors include: a monoalkylaminosilane precursor, a hydrazinosilane precursor, or combinations thereof.
  • the silicon-containing precursor comprises a monoalkylaminosilane precursor having at least one N-H fragment and at least one Si-H fragment.
  • Suitable monoalkylaminosilane precursors containing both the N-H fragment and the Si-H fragment include, for example: bis(tert-butylamino)silane (BTBAS), tris(tert-butylamino)silane, bis(iso-propylamino)silane, tris(iso-propylamino)silane, and mixtures thereof.
  • the monoalkylaminosilane precursor has the formula (R 7 NH) n SiR 8 m H 4-(n+m) wherein R 7 and R 8 are the same or different and independently selected from the group consisting of C 1-10 alkyl, vinyl allyl, phenyl, C 4-10 cyclic alkyl, C 1-10 fluoroalkyl, and C 1-10 silylalkyl and wherein n is a number ranging from 1 to 3, m is a number ranging from 0 to 2, and the sum of "n + m" is a number that is less than or equal to 3.
  • the silicon-containing precursor comprises a hydrazinosilane having the formula (R 9 2 N-NH) x SiR 10 y H 4-(x+y) wherein R 9 and R 10 are same or different and independently selected from the group consisting of C 1-10 alkyl, vinyl, allyl, phenyl, C 4-10 cyclic alkyl, C 1-10 fluoroalkyl, C 1-10 silylalkyls and wherein x is a number ranging from 1 to 2, y is a number ranging from 0 to 2, and the sum of "x + y" is a number that is less than or equal to 3.
  • R 9 and R 10 are same or different and independently selected from the group consisting of C 1-10 alkyl, vinyl, allyl, phenyl, C 4-10 cyclic alkyl, C 1-10 fluoroalkyl, C 1-10 silylalkyls and wherein x is a number ranging from 1 to 2, y is a number ranging from 0 to 2,
  • Suitable hydrazinosilane precursors include, but are not limited to: bis(1,1-dimethylhydrazino)-silane, tris(1,1-dimethylhydrazino)silane, bis(1,1-dimethylhydrazino)ethylsilane, bis(1,1-dimethylhydrazino)isopropylsilane, bis(1,1-dimethylhydrazino)vinylsilane, and mixtures thereof.
  • the silicon-containing precursor may be introduced into the reactor at a predetermined molar volume, or from about 0.1 to about 1000 micromoles. In this or other embodiments, the silicon-containing precursor may be introduced into the reactor for a predetermined time period, or from about 0.001 to about 500 seconds.
  • the silicon-containing precursors react with the metal hydroxyl groups formed by the reaction of the metal amide with the oxygen source and become chemically adsorbed onto the surface of the substrate, which results in the formation of a silicon oxide or a silicon oxynitride via metal-oxygen-silicon and metal-oxygen-nitrogen-silicon linkages, thus providing the metal silicate or the metal silicon oxynitride film.
  • oxygen source may be introduced into the reactor in the form of at least one oxygen source and/or may be present incidentally in the other precursors used in the deposition process.
  • Suitable oxygen source gases may include, for example: water (H 2 O) (e.g., deionized water, purifier water, and/or distilled water), oxygen (O 2 ), oxygen plasma, ozone (O 3 ), nitric oxide (NO), nitrogen dioxide (NO 2 ), carbon monoxide (CO), carbon dioxide (CO 2 ) and combinations thereof.
  • the oxygen source comprises an oxygen source gas, that is introduced into the reactor at a flow rate ranging from about 1 to about 2000 square cubic centimeters (sccm) or from about 1 to about 1000 sccm.
  • the oxygen source can be introduced for a time that ranges from about 0.1 to about 100 seconds.
  • the oxygen source comprises water having a temperature of 10°C or greater.
  • the precursor pulse can have a pulse duration that is greater than 0.01 seconds
  • the oxidant pulse duration can have a pulse duration that is greater than 0.01 seconds
  • the water pulse duration can have a pulse duration that is greater than 0.01 seconds.
  • the deposition methods disclosed herein may involve one or more purge gases.
  • the purge gas which is used to purge away unconsumed reactants and/or reaction byproducts, is an inert gas that does not react with the precursors and may preferably be selected from: argon (Ar), nitrogen (N 2 ), helium (He), hydrogen (H 2 ) and mixture thereof.
  • a purge gas such as Ar, is supplied into the reactor at a flow rate ranging from about 10 to about 2000 sccm for about 0.1 to 1000 seconds, thereby purging the unreacted material and any by-product that remain in the reactor.
  • an additional gas such as a nitrogen source gas
  • nitrogen source gases may include, for example: NO, NO 2 , ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, and combinations thereof.
  • the temperature of the substrate in the reactor i.e., a deposition chamber
  • the pressure may range from about 0.1 Torr (13 Pa) to about 100 Torr (13 kPa) or from about 0.1 Torr (13 Pa) to about 5 Torr (0.7 kPa).
  • the respective step of supplying the precursors, the oxygen source, and/or other precursors or source gases may be performed by changing the time for supplying them to change the stoichiometric composition of the resulting metal silicate, metal silicon oxynitride film, or other metal-containing film.
  • Energy is applied to the at least one of the precursor, oxygen source gas, reducing agent, or combination thereof to induce reaction and to form the metal-containing film on the substrate.
  • energy can be provided by, but not limited to, thermal, plasma, pulsed plasma, helicon plasma, high density plasma, inductively coupled plasma, X-ray, e-beam, photon, and remote plasma methods.
  • a secondary radio frequency (RF) frequency source can be used to modify the plasma characteristics at the substrate surface.
  • the plasma-generated process may comprise a direct plasma-generated process in which plasma is directly generated in the reactor, or alternatively a remote plasma-generated process in which plasma is generated outside of the reactor and supplied into the reactor.
  • the Group 4 metal containing film is formed using a vapor deposition method that comprises the steps of: (a) introducing a Group 4 metal precursor in a vapor state into a reaction chamber and chemisorbing the Group 4 metal precursor onto a substrate which is heated; (b) purging away the unreacted Group 4 metal precursor; (c) introducing an oxygen source onto the heated substrate to react with the sorbed Group 4 metal precursor; and (d) purging away the unreacted oxygen source.
  • the above steps define one cycle for the method described herein; and the cycle can be repeated until the desired thickness of a metal-containing film is obtained.
  • the steps of the methods described herein may be performed in a variety of orders, may be performed sequentially or concurrently (e.g., during at least a portion of another step), and any combination thereof.
  • the respective step of supplying the precursors and the oxygen source gases may be performed by varying the duration of the time for supplying them to change the stoichiometric composition of the resulting metal oxide film.
  • a strontium-containing precursor, a barium-containing precursor or both precursors can be alternately introduced in step a into the reactor chamber.
  • the Group 4 metal precursor and/or other metal containing precursors may be delivered to the reaction chamber, such as a CVD or ALD reactor, in a variety of ways.
  • a liquid delivery system may be utilized.
  • a combined liquid delivery and flash vaporization process unit may be employed, such as, for example, the turbo vaporizer manufactured by MSP Corporation of Shoreview, MN, USA, to enable low volatility materials to be volumetrically delivered, leading to reproducible transport and deposition without thermal decomposition of the precursor. Both of these considerations of reproducible transport and deposition without thermal decomposition are essential for providing a commercially acceptable copper CVD or ALD process.
  • a cyclic deposition process such as CCVD, ALD, or PEALD may be employed, wherein a Group 4 metal precursor or its solution and an oxygen source, such as; for example, ozone, oxygen plasma or water plasma, are employed.
  • the gas lines connecting from the precursor canisters to the reaction chamber are heated to one or more temperatures ranging from about 150°C to about 200°C depending upon the process requirements, and the container of the Group 4 metal precursor is kept at one or more temperatures ranging from about 100°C to about 190°C for bubbling, wherein the solution comprising the Group 4 metal precursor is injected into a vaporizer kept at one or more temperatures ranging from about 150°C to about 180°C for direct liquid injection.
  • a flow of 100 sccm of argon gas may be employed as a carrier gas to help deliver the vapor of the Group 4 metal precursor to the reaction chamber during the precursor pulsing.
  • the reaction chamber process pressure is about 1 Torr (133 Pa).
  • the substrate such as silicon oxide or metal nitride
  • An inert gas such as argon gas, purges away unadsorbed excess complex from the process chamber.
  • an oxygen source is introduced into reaction chamber to react with the absorbed surface followed by another inert gas purge to remove reaction by-products from the chamber.
  • the process cycle can be repeated to achieve the desired film thickness.
  • the precursors described herein may be delivered in neat liquid form, or alternatively, may be employed in solvent formulations or compositions comprising same.
  • the precursor formulations may include solvent component(s) of suitable character as may be desirable and advantageous in a given end use application to form a film on a substrate.
  • the solvent employed in solubilizing the precursor for use in a deposition process may comprise any compatible solvent or their mixture, including; aliphatic hydrocarbons(e.g., pentane, hexane, heptane, octane, decane, dodecane, ethylcyclohexane, propylcyclohexane), aromatic hydrocarbons (e.g., benzene, toluene, ethylbenzene, xylene, mesitylene, ethyl toluene and other alkyl substituted aromatic solvents), ethers, esters, nitriles, alcohols, amines (e.g., triethylamine, tert-butylamine), imines and carbodiimides (e.g., N,N'-diisopropylcarbodiimide), ketones, aldehydes, amidines, guanadines, isourea
  • suitable solvents are selected from the group consisting of glyme solvents having from 1 to 20 ethoxy -(C 2 H 4 O)- repeat units (e.g. dimethoxyethane, 1,2 -diethoxyethane and diglyme); organic ethers selected from the group consisting of propylene glycol groups(e.g. dipropylene glycol dimethyl ether) ; C 2 -C 12 alkanols; organic ethers selected from the group consisting of dialkyl ethers comprising C 1 -C 6 alkyl moieties, C 4 -C 8 cyclic ethers (e.g.
  • organic amide class of the form RCONR'R" wherein R and R' are alkyl having from 1-10 carbon atoms and they can be connected to form a cyclic group via (CH 2 ) n , wherein n is from 4-6, preferably 5, and R" is selected from alkyl having from 1 to 4 carbon atoms and cycloalkyl.
  • R and R' are alkyl having from 1-10 carbon atoms and they can be connected to form a cyclic group via (CH 2 ) n , wherein n is from 4-6, preferably 5, and R" is selected from alkyl having from 1 to 4 carbon atoms and cycloalkyl.
  • N-methyl- or N-ethyl- or N-cyclohexyl-2-pyrrolidinones, N,N -Diethylacetamide, and N,N -Diethylformamide are examples.
  • a direct liquid delivery method can be employed by dissolving the Group 4 metal precursor in a suitable solvent or a solvent mixture to prepare a solution with a molar concentration from 0.01 to 2 M, depending the solvent or mixed-solvents employed.
  • the solvent employed herein may comprise any compatible solvents or their mixture including, but not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, linear or cyclic ethers, esters, nitriles, alcohols, amines, polyamines, aminoethers and organic amides, preferably a solvent with a high boiling point, such as octane, ethylcyclohexane, decane, dodecane, xylene, mesitylene and dipropylene glycol dimethyl ether.
  • the method described herein also includes a cyclic deposition process for the formation of ternary metal oxide films, wherein a plurality of precursors are sequentially introduced into a deposition chamber, vaporized and deposited on a substrate under conditions for forming a said ternary metal oxide film.
  • the resultant metal oxide films can be exposed to a post-deposition treatment, such as a plasma treatment to densify the film.
  • the method described herein may be used to deposit a metal-containing film on at least a portion of a substrate.
  • suitable substrates include, but are not limited to, semiconductor materials, such as strontium titanate, barium strontium titanate, yttrium oxide doped with titanium, lanthanum oxide doped with titanium, and other lanthanide oxides doped with titanium.
  • a colorless plate-like crystal of bis(ethoxy)bis(ethyl acetoacetate)titanium was structurally characterized by X-ray single crystal analysis. The structure is confirmed to be a monomer, i.e. the titanium atom is coordinated with two ethoxy and two ethyl acetoacetato ligands in a distorted octahedral environment in which the two ethoxy groups are cis to each other, the two methyl groups are trans to each other, and the two esterate groups are cis to each other.
  • a pale yellow block-like crystal of bis(methoxy)bis(methyl acetoacetate)titanium was structurally characterized by X-ray single crystal analysis.
  • the structure is confirmed to be a monomer, i.e. the titanium atom is coordinated with two methoxy and two methyl acetoacetato ligands in a distorted octahedral environment in which the two methoxy groups are cis to each other position, the two methyl groups are trans to each other, and the two esterate groups are cis to each other.
  • the melting point was measured by the Differential scanning calorimetry (DSC) at 10 C/min heating rate to be 51°C.
  • DSC Differential scanning calorimetry
  • TGA analysis shows less than 0.2 wt. % residue, implying that it can be used as a suitable precursor in a vapor deposition process.
  • a colorless plate-like crystal of bis(methoxy)bis(methyl 4,4-dimethyl-3-oxopentanoato)titanium was structurally characterized by X-ray single crystal analysis.
  • the structure shows the titanium atom is coordinated with two methoxy and two methyl 4,4-dimethyl-3-oxopentanoato ligands in a distorted octahedral environment as the two methoxy groups are cis to each other position, the two tert-butyl ( t Bu) groups are trans to each other, and the two esterate groups are cis to each other.
  • DSC at 10 C/min in a pressurized pan shows no thermal effects due to decomposition up to ⁇ 270°C.
  • TGA analysis shows that it leaves almost no residue, implying that it can be used as a suitable precursor in a vapor deposition process.
  • DSC data show better thermal stability of bis(ethoxy)bis(ethyl 4,4-dimethyl-3-oxopentanoato) titanium where the R 2 group (Formula A) is a branched alkyl (exotherm onset is 310 °C) compare to bis(ethoxy)bis(ethyl acetoacetato)titanium where R 2 group (Formula A) is a linear alkyl (exotherm onset is 278 °C).
  • DSC data show better thermal stability of bis(ethoxy)bis(ethyl 4,4-dimethyl-3-oxopentanoato) titanium where the R 2 group (Formula A) is a branched alkyl (exotherm onset is 298 °C) compare to bis(ethoxy)bis(ethyl acetoacetato)titanium where R 2 group (Formula A) is a linear alkyl (exotherm onset is 253 °C).
  • Viscosity was measured using an AR-G2 rheometer (TA Instruments, New Castle, DE). Temperature was controlled at desired temperature using a Peltier heating element. A 60 mm diameter parallel plate geometry was used. After sample loading, 600 sec was allowed for thermal equilibration before a shear rate sweep measurement. Viscosities were measured at shear rates ranging from 1 to 100 s -1 . Bis(ethoxy)bis(ethyl 4,4-dimethyl-3-oxopentanoato) titanium showed Newtonian behavior, with a viscosity of 107.9 centipoise at 25 °C and 10.1 centipoise at 80 °C.
  • the viscosity of bis(ethoxy)bis(ethyl 4,4-dimethyl-3-oxopentanoato) titanium can be decreased below 10 centipoise at 25 °C by using an additive having low viscosity, for example octane.
  • This example describes surface thermal reactivity studies using bis(methoxy)bis(methyl 4,4-dimethyl-3-oxopentanoato)titanium.
  • the deposition temperature range is 200 ⁇ 400 °C.
  • the deposition chamber pressure ranges around 1.5 Torr (200 Pa).
  • the container for bis(methoxy)bis(methyl 4,4-dimethyl-3-oxopentanoato)titanium was kept at 120°C.
  • One cycle of the surface reactivity consists of 2 steps.
  • This example describes surface thermal reactivity studies using bis(methoxy)bis(methyl 4,4-dimethyl-3-oxopentanoato)titanium.
  • the deposition temperature range is 200 ⁇ 400 °C.
  • the deposition chamber pressure ranges around 1.5 Torr (200 Pa).
  • the container for bis(methoxy)bis(methyl 4,4-dimethyl-3-oxopentanoato)titanium was kept at 150°C.
  • One cycle of the surface reactivity consists of 2 steps.
  • This example describes an ALD or CCVD deposition of TiO 2 using bis(methoxy)bis(methyl 4,4-dimethyl-3-oxopentanoato)titanium and ozone.
  • the deposition temperature range is 200 ⁇ 400 °C.
  • the container for bis(methoxy)bis(methyl 4,4-dimethyl-3-oxopentanoato)titanium was kept at 120°C.
  • One cycle of ALD or CCVD of TiO 2 consists of 4 steps.
  • This example describes an ALD or CCVD deposition of TiO 2 using bis(ethoxy)bis(ethyl 4,4-dimethyl-3-oxopentanoato)titanium and ozone.
  • the deposition temperature range is 200 ⁇ 400 °C.
  • the container for bis(methoxy)bis(methyl 4,4-dimethyl-3-oxopentanoato)titanium was kept at 120°C.
  • One cycle of ALD or CCVD of TiO 2 consists of 4 steps.
  • the typical ALD conditions are: Ti precursor pulse time was 4 or 8 seconds, the Ar purge time after Ti precursor pulse was 10 seconds, the ozone pulse time was 5 seconds, and the Ar purge time after ozone pulse was 10 seconds.
  • the cycle was repeated 100 times.
  • TiO 2 films were obtained and the dependence of titanium oxide thickness on deposition temperature is shown in Figure 8 .
  • the results suggests that ALD thermal process window can be up to ⁇ 375 °C with ALD rate ⁇ 0.5 A/cycle (0.05 nm/cycle).
  • This example describes an ALD deposition of TiO 2 using bis(ethoxy)bis(ethyl 4,4-dimethyl-3-oxopentanoato)titanium and ozone on a trench pattern wafer with a spacing of around 550 ⁇ (55 nm), an aspect ratio of 20 to 1, and silicon nitride on the surface.
  • the deposition temperature was 375°C.
  • the deposition chamber pressure was around 1.0 Torr (133 Pa).
  • the container for bis(ethoxy)bis(ethyl 4,4-dimethyl-3-oxopentanoato)titanium was kept at 150°C.
  • FIG. 9 shows the Transmission Electron Microscope (TEM) of the deposited TiO 2 film with a thickness of 8.9 ⁇ 0.5 nm at the top of the trenches, 8.8 ⁇ 0.5 nm at the top corner of the trenches, 8.7 ⁇ 0.5 nm at middle of the trenches, and 8.2 ⁇ 0.5 nm at the bottom of the trenches, demonstrating excellent step coverage ( >90%) from the top to the bottom of the patterned substrate.
  • TEM Transmission Electron Microscope

Claims (15)

  1. Gruppe-4-Metall-Vorläufer, repräsentiert durch die folgende Formel:
    Figure imgb0014
     wobei M ein Gruppe-4-Metall ist, das aus der Gruppe ausgewählt ist, bestehend aus Ti, Zr und Hf;
    wobei R1 aus der Gruppe ausgewählt ist, bestehend aus linearen oder verzweigten C1-10Alkylen und C6-12 Arylen;
    wobei R2 aus der Gruppe ausgewählt ist, bestehend aus verzweigten C3-10 Alkylen und C6-12 Arylen;
    wobei R3 aus der Gruppe ausgewählt ist, bestehend aus Wasserstoff, C1-10 Alkylen und C6-12 Arylen; und
    wobei die R1-Gruppen gleich sind.
  2. Vorläufer nach Anspruch 1, wobei R1 aus der Gruppe ausgewählt ist, bestehend aus linearen C1-10 Alkylen.
  3. Vorläufer nach Anspruch 1 oder 2, wobei R1 aus der Gruppe ausgewählt ist, bestehend aus Methyl, Ethyl und n-Propyl.
  4. Vorläufer nach einem der vorhergehenden Ansprüche, wobei R2 aus der Gruppe ausgewählt ist, bestehend aus iso-Propyl, tert-Butyl, sec-Butyl, iso-Butyl und tert-Amyl.
  5. Vorläufer nach einem der vorhergehenden Ansprüche, wobei R2 tert-Butyl ist.
  6. Vorläufer nach einem der vorhergehenden Ansprüche, wobei R3 aus der Gruppe ausgewählt ist, bestehend aus Wasserstoff und Methyl.
  7. Vorläufer nach einem der vorhergehenden Ansprüche, wobei R3 Wasserstoff ist.
  8. Vorläufer nach einem der vorhergehenden Ansprüche, wobei M Titan ist.
  9. Vorläufer nach Anspruch 1, wobei M Zirconium und R1 aus der Gruppe ausgewählt ist, bestehend aus verzweigten C3-10 Alkylen.
  10. Vorläufer nach einem der vorhergehenden Ansprüche in der Form einer Lösung in Kombination mit einem Lösungsmittel.
  11. Vorläufer nach Anspruch 10, wobei das Lösungsmittel aus der Gruppe ausgewählt ist, bestehend aus Octan, Ethylcyclohexan, Dodecan, Toluol, Xylen, Mesitylen, Diethylbenzen und Mischungen davon.
  12. Verfahren zur Abscheidung eines Gruppe-4-Metall-haltigen Films umfassend:
    die Verwendung eines Gruppe-4-Metall-Vorläufers, repräsentiert durch die folgende Formel:
    Figure imgb0015
     wobei M ein Gruppe-4-Metall ist, das aus der Gruppe ausgewählt ist, bestehend aus Ti, Zr und Hf;
    wobei R1 aus der Gruppe ausgewählt ist, bestehend aus linearen oder verzweigten C1-10Alkylen und C6-12 Arylen;
    wobei R2 aus der Gruppe ausgewählt ist, bestehend aus verzweigten C3-10 Alkylen und C6-12 Arylen;
    wobei R3 aus der Gruppe ausgewählt ist, bestehend aus Wasserstoff, C1-10 Alkylen und C6-12 Arylen; und
    wobei die R1-Gruppen gleich sind.
  13. Verfahren nach Anspruch 12, wobei der Gruppe-4-Metall-Vorläufer wie in einem der Ansprüche 2 bis 11 definiert ist.
  14. Verfahren nach Anspruch 12 oder 13, umfassend das Reagieren des Gruppe-4-Metall-Vorläufers mit mindestens einem weiteren Metall-Vorläufer, wobei das Metall von dem mindestens einen weiteren Metall-Vorläufer aus der Gruppe 2 bis 16 ausgewählt ist, wobei ein oder mehrere der Liganden des mindestens einen weiteren Metall-Vorläufers aus der Gruppe ausgewählt sind, bestehend aus β-Diketonaten, β-Diketoesterat, β-Ketoiminaten, β-Diiminaten, Alkylen, Carbonyl, Alkylcarbonyl, Cyclopentadienylen, Pyrrolyl, Imidazol, Amidinat, Alkoxy und Mischungen davon, wobei die Liganden einer der folgenden sind: Monodentat, Bidentat oder Multidentat.
  15. Verfahren nach Anspruch 14, wobei der mindestens eine weitere Metall-Vorläufer aus der Gruppe ausgewählt ist, bestehend aus: Bis(2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanonato-N,O,N')strontium, Bis(2,2-dimethyl-5-(1-dimethylamino-2-propylimino)-3-hexanonato-N,O,N')strontium, Tetraktis(2,2,6,6-tetramethyl-3,5-heptandionato)cer (IV), Tris(2,2,6,6-tetramethyl-3,5-heptandionato)lanthan, Sr[(tBu)3Cp]2, Sr[(iPr)3Cp]2, Sr[(nPrMe4Cp]2, Ba[(tBu)3Cp]2, LaCp3, La(MeCp)3, La(EtCp)3, La[(iPrCp)3, Zirconium-tert-butoxid, Strontium-bis(2-tert-butyl-4,5-di-tert-amylimidazolat), Barium-bis(2-tert-butyl-4,5-di-tert-amylimidazolat) und Barium-bis(2,5-di-tert-butyl-pyrrolyl).
EP10188585.3A 2009-10-23 2010-10-22 Gruppe-4-Metallvorläufer für metallhaltige Filme Active EP2322530B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US25425309P 2009-10-23 2009-10-23
US12/904,421 US8952188B2 (en) 2009-10-23 2010-10-14 Group 4 metal precursors for metal-containing films

Publications (3)

Publication Number Publication Date
EP2322530A2 EP2322530A2 (de) 2011-05-18
EP2322530A3 EP2322530A3 (de) 2011-06-15
EP2322530B1 true EP2322530B1 (de) 2016-04-06

Family

ID=43466743

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10188585.3A Active EP2322530B1 (de) 2009-10-23 2010-10-22 Gruppe-4-Metallvorläufer für metallhaltige Filme

Country Status (6)

Country Link
US (1) US8952188B2 (de)
EP (1) EP2322530B1 (de)
JP (1) JP5469037B2 (de)
KR (3) KR20110044724A (de)
CN (1) CN102040620B (de)
TW (1) TWI454589B (de)

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014525513A (ja) * 2011-09-07 2014-09-29 ダウ コーニング コーポレーション ハフニウム含有錯体及び縮合反応触媒、該触媒の調製方法、及び該触媒を含有する組成物
JP6012055B2 (ja) 2011-09-07 2016-10-25 ダウ コーニング コーポレーションＤｏｗ Ｃｏｒｎｉｎｇ Ｃｏｒｐｏｒａｔｉｏｎ チタン含有錯体及び縮合反応触媒、該触媒の調製方法、及び該触媒を含有する組成物
EP2753663B1 (de) 2011-09-07 2020-01-08 Dow Silicones Corporation Zirkoniumhaltiger komplex und kondensationsreaktionskatalysatoren, verfahren zur herstellung der katalysatoren und zusammensetzungen mit den katalysatoren
GB201116025D0 (en) 2011-09-16 2011-10-26 Surface Innovations Ltd Method
US9139699B2 (en) 2012-10-04 2015-09-22 Dow Corning Corporation Metal containing condensation reaction catalysts, methods for preparing the catalysts, and compositions containing the catalysts
US20130260025A1 (en) * 2012-03-30 2013-10-03 Air Products And Chemicals, Inc. Group 2 Imidazolate Formulations for Direct Liquid Injection
US9404175B2 (en) 2013-02-04 2016-08-02 Blackberry Limited Method of forming a target for deposition of doped dielectric films by sputtering
US20140225232A1 (en) * 2013-02-08 2014-08-14 Taiwan Semiconductor Manufacturing Company Limited Reducing contamination during atomic layer deposition
JP2014216647A (ja) * 2013-04-29 2014-11-17 エーエスエムアイピー ホールディング ビー．ブイ． 金属ドープされた抵抗切り替え層を有する抵抗変化型メモリを製造する方法
CN104945444A (zh) * 2014-03-26 2015-09-30 广东丹邦科技有限公司 用于制备钡金属茂合物的原料及钡金属茂合物的制备方法
KR102147190B1 (ko) * 2015-03-20 2020-08-25 에스케이하이닉스 주식회사 막형성조성물 및 그를 이용한 박막 제조 방법
US20170107612A1 (en) * 2016-12-30 2017-04-20 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Zirconium, hafnium, titanium precursors and deposition of group 4 containing films using the same
US10364259B2 (en) * 2016-12-30 2019-07-30 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Zirconium, hafnium, titanium precursors and deposition of group 4 containing films using the same
US10337104B2 (en) * 2016-12-30 2019-07-02 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Zirconium, hafnium, titanium precursors and deposition of group 4 containing films using the same
US11081337B2 (en) * 2017-03-15 2021-08-03 Versum Materials U.S., LLC Formulation for deposition of silicon doped hafnium oxide as ferroelectric materials
WO2019238261A1 (en) * 2018-06-15 2019-12-19 Ramirez Rios Liliana Patricia METAL COMPLEXES OF β-DIKETONES AND/OR POLYPHENOLS BY GREEN CHEMISTRY, PREPARATION METHOD THEREOF, SUNSCREEN THEREOF, SKIN OR HAIR TONE CONCEALER THEREOF, HAIR DYEING THEREOF AND OTHER USES THEREOF
US11274363B2 (en) 2019-04-22 2022-03-15 Nxp Usa, Inc. Method of forming a sputtering target
JP7353200B2 (ja) 2020-02-06 2023-09-29 東京エレクトロン株式会社 成膜方法
US11967502B2 (en) 2020-06-30 2024-04-23 Samsung Electronics Co., Ltd. Methods of forming material layer, semiconductor devices, and methods of manufacturing the same

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0940683A (ja) * 1995-07-31 1997-02-10 Mitsubishi Materials Corp 高純度Ｔｉ錯体及びその製造方法並びにＢＳＴ膜形成用液体組成物

Family Cites Families (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
HU199679B (en) 1983-02-09 1990-03-28 Byk Gulden Lomberg Chem Fab Process for producing new complex compounds and antineoplastic compositions containing them
JPS6356530A (ja) 1986-08-27 1988-03-11 Nissan Chem Ind Ltd 新規なるチタノシロキサン重合体の製造法
US5840897A (en) 1990-07-06 1998-11-24 Advanced Technology Materials, Inc. Metal complex source reagents for chemical vapor deposition
JP3883235B2 (ja) 1996-10-08 2007-02-21 株式会社Ａｄｅｋａ 金属錯体化合物からなるｃｖｄ材料
GB9709639D0 (en) * 1997-05-14 1997-07-02 Inorgtech Ltd Chemical vapour deposition precursors
US6117487A (en) 1998-04-02 2000-09-12 Asahi Denka Kogyo Kabushiki Kaisha Process for forming metal oxide film by means of CVD system
DE60104650T2 (de) 2000-01-06 2005-07-28 Dow Corning S.A. Organosiloxan-zusammensetzungen
JP4614499B2 (ja) * 2000-04-20 2011-01-19 ダウ コーニング コーポレーション 硬化性組成物
JP4400983B2 (ja) * 2000-01-06 2010-01-20 東レ・ダウコーニング株式会社 硬化性組成物
KR100435816B1 (ko) 2001-01-19 2004-06-12 한국과학기술연구원 화학증착용 유기티탄 전구체 및 그의 제조 방법
DE02772548T1 (de) * 2001-10-26 2004-11-11 Epichem Ltd., Wirral Vorlaeuferverbindungen für chemische dampfphasenabscheidung
KR200280361Y1 (ko) 2002-04-10 2002-07-02 남병성 교자상을 겸한 식탁
US6562990B1 (en) 2002-07-03 2003-05-13 E. I. Du Pont De Nemours And Company Titanium chelates and processes therefor
EP1698614B1 (de) * 2003-12-25 2011-07-13 Adeka Corporation Metallverbindung, material zur ausbildung eines dünnen filmes und verfahren zur herstellung eines dünnen filmes
WO2005108493A1 (ja) * 2004-05-07 2005-11-17 Kaneka Corporation 硬化性組成物
JP4656292B2 (ja) * 2004-09-10 2011-03-23 日産化学工業株式会社 金属のアルカノールアミン化合物の製造法
JP2007197804A (ja) * 2006-01-30 2007-08-09 Mitsubishi Materials Corp 有機金属化学蒸着法用原料及び該原料を用いた金属含有膜の製造方法
US7947814B2 (en) 2006-04-25 2011-05-24 Air Products And Chemicals, Inc. Metal complexes of polydentate beta-ketoiminates
US20080254218A1 (en) 2007-04-16 2008-10-16 Air Products And Chemicals, Inc. Metal Precursor Solutions For Chemical Vapor Deposition
CN100590803C (zh) 2007-06-22 2010-02-17 中芯国际集成电路制造(上海)有限公司 原子层沉积方法以及形成的半导体器件
US7691984B2 (en) 2007-11-27 2010-04-06 Air Products And Chemicals, Inc. Metal complexes of tridentate β-ketoiminates
JP2009170439A (ja) 2008-01-10 2009-07-30 Panasonic Corp ゲート絶縁膜の形成方法
US8168811B2 (en) 2008-07-22 2012-05-01 Advanced Technology Materials, Inc. Precursors for CVD/ALD of metal-containing films
US20100119726A1 (en) 2008-11-07 2010-05-13 Air Products And Chemicals, Inc. Group 2 Metal Precursors For Deposition Of Group 2 Metal Oxide Films
US8471049B2 (en) 2008-12-10 2013-06-25 Air Product And Chemicals, Inc. Precursors for depositing group 4 metal-containing films

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0940683A (ja) * 1995-07-31 1997-02-10 Mitsubishi Materials Corp 高純度Ｔｉ錯体及びその製造方法並びにＢＳＴ膜形成用液体組成物

Also Published As

Publication number Publication date
EP2322530A3 (de) 2011-06-15
JP2011121936A (ja) 2011-06-23
JP5469037B2 (ja) 2014-04-09
CN102040620A (zh) 2011-05-04
EP2322530A2 (de) 2011-05-18
KR20130093579A (ko) 2013-08-22
CN102040620B (zh) 2014-09-03
US8952188B2 (en) 2015-02-10
US20110250126A1 (en) 2011-10-13
KR20160076503A (ko) 2016-06-30
KR20110044724A (ko) 2011-04-29
TW201118193A (en) 2011-06-01
TWI454589B (zh) 2014-10-01

Similar Documents

Publication Publication Date Title
EP2322530B1 (de) Gruppe-4-Metallvorläufer für metallhaltige Filme
US8962875B2 (en) Metal-enolate precursors for depositing metal-containing films
US8471049B2 (en) Precursors for depositing group 4 metal-containing films
KR101749783B1 (ko) 증착용 티타늄 함유 전구체
KR20130027578A (ko) 유전체 필름의 형성 방법, 신규 전구체 및 그의 반도체 제조에서의 용도
JP2011117081A (ja) 第４族金属含有膜を堆積させるための液体前駆体
US8691710B2 (en) Group IV metal complexes for metal-containing film deposition
JP5373945B2 (ja) 第四族金属含有フィルムの堆積方法
EP2708542A1 (de) Bariumvorläufer des Salen-Typs für den Dampfphasenauftrag dünner Schichten
EP2708543A1 (de) Strontiumvorläufer des Salen-Typs für den Dampfphasenauftrag dünner Schichten

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

17P Request for examination filed

Effective date: 20111110

17Q First examination report despatched

Effective date: 20130417

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20151019

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 787708

Country of ref document: AT

Kind code of ref document: T

Effective date: 20160415

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602010032003

Country of ref document: DE

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

Ref country code: NL

Ref legal event code: MP

Effective date: 20160406

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 787708

Country of ref document: AT

Kind code of ref document: T

Effective date: 20160406

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160406

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160806

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160406

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160406

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160706

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160406

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160406

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160406

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160406

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160707

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160406

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160406

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160406

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160808

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160406

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160406

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602010032003

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160406

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160406

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160406

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160406

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160406

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160406

26N No opposition filed

Effective date: 20170110

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160406

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20161022

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20161031

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20161022

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20161031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20161022

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20161022

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20101022

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160406

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160406

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160406

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160406

Ref country code: MT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20161031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160406

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160406

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230602

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20230911

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20230906

Year of fee payment: 14